Triazone ring compound



.01 more widely useful ?atented June 35, 1943 gton, Del, a corporation 08 Delaware mo a Com .cv

No Drawing. Application Earmary 15, 1942, Serial No. 426,905

10 Claims. in. 260-=24B) iently and economically from urea, formaldehyde,

and primary. amines. solid but quite unstable not very reactive.

These compounds are to heat, and generally They have therefore not been very widely utilized.

This invention has as an object the preparation compounds from tetrahydrotriazones. A further object comprises new textile modifying agents, new polymer components and new plasticizersfor cellulose, cellulose derivatives, e. g. the acetate, butyrate, and ethylcellulose, polyamides, etc. Other objects will appear hereinafter.

- These objects are accomplished by the following invention of compounds of the formula Room A \NCH R HI UH: N i. where R and R are monovalent aliphatic hydrocarbon radicals which may be saturated or unsaturated, acyclic or cyclic, unsubstituted or substituted by inert groups such as hydroxy, alkoxy, aryl, etc, and X is a chalcogen of atomic 4 less than 33 and their preparation by reacting a tetrahydrotriazone with formaldehyde and then with an alcohol. i

The products of this invention are relatively stable, water-white liquids. They possess characteristic odors resembling those of the aliphatic amines. The lower members are soluble lib water, alcohols, esters, higher members are not soluble. in water and are more soluble in hydrocarbons. some or the products of this invention, e. g.'those contaizzgig hydrom; substituted aliphatic groups in the 5 50- sition, are quite viscous. The lower molec ar weight members having no substituted hydroxyl or similar groups are quite fluid.

The N,N'-(alkoxymethyl)tetrahydrotriazones and acetone whereas the last step.

are made by first reacting the appropriate tetrahydrotriazone with aqueous formaldehyde and then adding an excess of an alcohol which reacts with the dimethylol derivative to give. the desired product. Basic catalysts are used 'in' the first stage, whereas acidicbatalysts are used in the The temperature used to BflGCt the reaction between the tetrahydrotriazone and formaldehyde may vary from o to 100 C. The time required depends upon the temperature used and hence may vary from 15 minutes to a fewdays. It is preferred to use a temperature oi -100 C. and a reaction time oi 15 minutes to 24 hours. The reaction between the alcohol and the dim'ethylol derivative of the tetrahydrotriazone may be carried out at temperatures of 0-l00 C., but temperatures of 25-50 C. are preierred because of the undesirable side reactions produced at higher temperatures.

The molar ratio of formaldehyde to tetrahye drotrlazone should be at least 2:1. The molar ratio of alcohol. to the dimethylol tetrahydrotriazone should also be at least 2:1, but it is preferred that a larger excess of alcohol be used inorder to reduce the concentration 0! water and thus efi'ect more nearly complete reaction.

It is preferred to concentrate the aqueous solution of the dimethylol derivative of the tetraweight hydrotriazone before adding the alcohol since this reduces the qulred.

The dimethylol derivative of tetrahydrotriazone may be made. using other forms of formaldehyde such as para-formaldehyde and trioxane and solvents other than water such as amount oi excess alcohol reethanol, methanol, dioxane, etc. By carrying out,

the addition of formaldehyde to the tetrahydrotriazone-in an alcohol solution the desired alkoxymethyl derivative can readily be obtained by subsequent acidification. 'of the medium.

The desired product can be preparedwithout isolating any of the intermediate compounds:

that is, a solution of the tetrahydrotriazone can be made by any of theproceduresdescribed in copending application Serial No. April 25, 1940by W. J. Burke. treatment of this solution with formaldehyde and an alcohol results in the formation 0! the N,N'ebi:; (alkoxymethyl) derivative.

reaction i The subsequent original weight of, yarn.

respects, 1. Resistance to creation-Treated and un-' The desired product can be obtained without forming the tetrahydrotriazone as an intermediate; that is, urea and formaldehyde may be reacted in such proportions that a tetramethylolurea is first formed, which can then be reacted with the appropriate primary amine to give the dimethylol derivative of the tetrahydrotriazone, which on subsequent treatment with an alcohol gives the N,N'-(alkoxymethyl) derivative. Another route to the desired product consists in reacting the appropriate dlalkyl ether of dimethylolurea with iormaldehyde and treating this product with the appropriate primary amine.

The more detailed practice the invention is illustrated by the following examples wherein the parts given are by weight. There are, of course, many forms of the invention other than these specific embodiments.

EXAMPLE I.--Tetrahudro-1,3-bis-(methorumethyl) --meth1lZ-2(1) -s-triazone A mixture of 40 parts of tetrahydro-figmethyl- 2-(1).-s-triazone, 83 parts'of 37% aqueous rormaldehyde, and 1.9 parts or barium hydroxide is minutes during which time the spontaneously to 40 C. The mixture is heated at 70-80 C. for 15 minutes and then concentrated to about eighty parts of a viscous syrup under reduced pressure at about 50 0. Two hundred and eighty parts of meth-" anol containing 2.! parts of concentrated hydrochloric acid is added and the mixture allowed to stand for approximately two hours. After neu tralizing the hydrochloric acid with sodium carbonate, the methanol is evaporated and the residue dissolved in chloroform. The insoluble material is filtered oil! and the solvent removed by distillation. Forty-five parts (64% yield) of tetrahydro Lii-bis (methoxymethyl) 5-methyl- 2(1) -s-triazone, a water-white mobile liquid distilling at 12o-122c./2-3 mm.,is obtained. This compound is soluble in water, ethanol, chloroform. and benzene and insoluble in paraflin hydrocarbons such as petroleum ether;

stirred for a few temperature rises Hydro gen Analysis Carbon Nitrogen Found 47. 50 7. 02 Calculated i0]: CsH|1N O| 47. 29 8. 38

Textiles may be advantageously modified by treatment with this product. A typical treatment is as follows: ten parts of tetrahydro-l,3- bisHmethoxymethyl) -5 methyl-2(1) -s-triar0ne, 2 arts or acetic acid. and 0.4 part or p-toluenesulfonic acid are dissolved in 87.6 parts of water. A skein of viscose rayon yarn (150 denier, 40 filament) of parts in weight is immersed in this solution and then dried by centrifuging and exposing-to air at room temperature. The dried skein is heated to 140 0. 1or 3 minutes, in'mild soap solution at 70 C., rinsed, and dried. Its weight is now 10.! parts: the increase in weight corresponds to a gain of 1%. based on the The treated yarn is superior to an untreated yarn control in several indicated by the followin tests:

,treated yarns which have been conditioned at 25 C. and 50% relative humidity are wound separately over a double-edged knife blade under a uniform tension of 50 g. After minutes, the tension is released and each thread cut along one edge of the knife blade. The crez'sed segments of the yarn are allow to relax for l l minutes while lying on a horizontal, smooth surface. The degree that the thread recovers from the creasing is an index of its resilience, and the angle formed by the thread is known as the crease angle. For treated yarn the crease angle is 122, whereas for untreated yarn it is 95; thus, with reference to the untreated yam, the geated yarn is 28% better in resistance to creas- 10 8.

2. Elastic recowriL-Segments of treated and untreated yarn which are 4.000" in length are rapidly stretched by 4% (i. e., to 4.160") and held in the elongated position for 100 seconds he- 15 foretension is released. After releasing the tension, the treated yarn spontaneously contracts 0.091" during the first 60 seconds, whereas the untreated yarn contracts only 0.077" in this same period of time. The relative superiority in elastic recovery conferred by this treatment is thus 3. Swellino.-Skeins of treated and untreated yarns of known weight are conditioned at C. and 50% relative humidity until they are constant in weight. They are thoroughly wet th water. subjected to a short centrifugation and then quickly weighed in a covered dish. The

gain in weight of untreated yarn is 100%, while the treated yam gains only 54% in weight. Relative to untreated yarn, the swellability is reduced by 85%. This modification in properties is accompanied by great improvement in the ease and rapidity of drying of treated fabrics, e. g.,

after dyeing or laundering procedures.

Exmru Il.Tetrahydro-1 ,3-bis-(metfiorymethyl) -5-beta-hudro.cuethul-2 (1) -s-triazone A mixture of 80 parts of tetrahydro-S-betahydroxyethyl-2(1) -s-triazone, 95 parts of 37% 40 aqueous formaldehyde, and 1.5 parts of barium hydroxide is stirred for 30 minutes during which time the temperature C. The mixture is then heated at 83 C. for 15 minutes, and cooled to room temperature. Four hundred and eighty parts or methanol containing 5.5 parts of hydrogen chloride is added and the mixture allowed to stand 20 minutes. After neutralizing the acid, the methanol is evaporated and the residue dissolved in chloroform. A small 9' amount 0! insoluble material is filtered oil and the chloroform'and removed by distillation at low pressure. 'The residue, tetrahydro-1,3-bis-(methoxymethyD-5- .beta-hydroxyethyl-2(1)-s-trlazone, is a viscous; slightly yellow liquid, soluble in water, alcohol,

benzene, and ethyl acetate but insoluble in petroleum ether. The yield is 06 parts.- Y

6 Analysis I Carbon gen Nitrogen Found .l 4a to s. 42 1a m Calculated for Coil |NsO|---.'. 46. 4 8. 2 18.0

Wan 11I.Te1.rahiuiro 1,3 bis (methmmethill) -5-ie0but1il-2- (1)-s-triaz0ne 'A mixture of 47.1 parts of tetrahydro-S-isobutyl-2-(1) -s-triazone, 100 parts o37% aqueous formaldehyde, 2 parts of barium hydroxide is he .ed at 80-00 C. for 10 minutes and then cooled to room temperature. Eight hundred (800) parts or methanol-containingl2 parts of concentrated hydrochloric acid is added and the 7s mixture allowed to stand 5 hours. After'neu rises spontaneously to 40 other low-boiling material methyD --isobutyl-2(l) s triazone,

'laaeroee f 3 tr the acid the methanol is evaporated and the residue lved in chloroform. A all amount oi insoluble material is filtered oil and the chloroform and other low-boiling material removed by distillation at low pr. Twen- 5 ty-two (22) parts oi tetrahydro-m-bls-methoxya terwhite mobile liquid. distilling at rec-145 6J5 mm. is obtained. This compound is soluble in waten'ethanol, chloroform, and benzenehut in- 10 in the process oi this invention a tetrahydrce wherein R is an aliphatic'monovalent hydrocar- 0 bon radical which may be substituted or unsubstituted, saturated or unsaturated, and X is either owsen or sulfur, is reacted at 0-100 -C., but preierably at -l00 C.. in the presence of a basic catalyst with formaldehyde, then at 0-100" (3., but preferably at 25-59 C., in the presenceoi an acidic catalyst, the resulting'product is reacted with an alcohol. I

any tetrahydrotriaaone of the above iormula may be used including: tetrahydro-o-methyl- 40 2(l)-s'-triazone, tetdro-S-beta-hydroxyethyl-2(l) -s-triazone, tetrahydro-5-tert. butyl-2(l) 's-triazone, tetrahydro-h-benayl-Ml)-s-triarone,

tetrahydro- 5, dimethylaminoethyl 2(1) s-trlazone, tetrahydro-5-allyl-2(1)-s-triazone, tetras5 hydro-5-methyl-2-thio -2U) -s-triazone, tetany alcoholROH may be employed in which 59 R is an aliphatic monovalent hydrocarbon radical which maybe saturated or unsaturated, acylic or cyclic, unsubstituted or substituted by groups such as hydroxy, alhoxy, aryl, dialkylamino, etc.

which are unreactive under the conditions of the reaction. The chain or carbon atoms may be interrupted by heteroatbms such as oxygen or,

.suliur. Alcohols which may be employed include methyl. yl. prop l. iso opy butyl. sob tr tert.-butyl, octyl. dodecyl. heta-hydrox'yethyl. 6o

methoxymethyl,

ethoethyl, met thyl, ethoxyethyl, butoxye'thyl, benwl, allyl; and cy-i. clohexyl alcohols, i. e., alcohols free from reactive sroupsother than hydrozyl.

The first stage oi the process, 1. e., the reaction with iormaldhyde, is carried out preferably in the presence oi a basic catalyst. i. e., any sub-- stance capable oi. eflectina a PH 01 greater than 7 when dissolved in water, e. g. triethye,

pyridine, CMOHM, NaQE, KOH, M8(OH)2', etc.

The second stase. i. e,. the reaction or tm di methyloltetrahydrot 1- with the alcohol is carried out in the h rso of acidic cat, i.

W04, mmiic acid, citric acid, Nail-I504, mmroi, etc.

The, general formula for the tetrahydro-1,3-

his-(alkoxymethyD-S substituted 2(1) s triazonesoi this invention is as follows:

. H30 R where X is a chalcogen of atomic weight less than 33, i. e., oxygen or sulfur, R and R are monovalent aliphatic hydrocarbon radicals which may be saturated or unsaturated, substituted or unsub-.

stituted as previously pointed out by groups which do not interfere with the present reaction such as alkoxy,.hydi'oxy,,or aryl groups,

The compounds of this invention may also he defined as tetrahydrotriazones having attached to the two carbon a chalcogen of atomic weight.

less than 33, on the 5 nitrogen. a monovalent hydrocarbon radical Joined thereto by a terminal aliphatic carbon, and on the 1 and 3 nitrogens monovalent radicals consisting of a monovalent hydrocarbon radical joined by a terminal aliphatic carbon thereof to an oxygen which is in turn joined, through a methyleneiCHs) group, to said nitrogens. The 4. and 6 carbons have their extranuclear velences sat atoms. Monovalent substituents on the 5 nitrogen and on the oxygen of, the cxymethyl groups attached to the 1 and 3 nitrogens which consist of hrbon radicals suhstltutedand/cr interrupted hyinert groups such as ether, hydroxy and the like are equivalent, for the purposes of this invention, to the simple hydrocarbon radicals. The inventionthus includes the following: tetrahydm -1,3- bis- (ethoethyl) -5-meth yi-2- (1) -s-triazone, tetrahydro 1,3 his (propoxymethyl) -5-ethy1-2( ),-s-trine, tetrahydro-LIibis- (isopropoethyl) 5-;butyl-2( 1) l-s-t'riazone, tetrahydro 1,3 bis- ,(isohutoethyl) -5-cyclohexyl 2(1) -s-triazone, toxymethyl) 5 methyl-2(1) -s-triazo'ne, tetrahydro-lfi-bis-(octoxymethyb -5- propyl-2(1)-striazone, tetrahydro-1,3 -bis- -(undecoxymethyl)- 5-isobutyl-2(1)-s-triazone, ietrahydro 1,3 his- (tertbutoxymethyl) 5 methyl-2(1) -s-trlazone and tetrahydro- 1,3 -bis-(sec-hutoxymethyl) -5- ethyl-2(1) -s-triazone, tetr; dro-1',3-bis-(allyloxymethyl) -metliyl-2(1) -s-triazone, tetrahy- -dre-1,8-bis-'(crotyloiwmethyl) 5 butyl-2 1) -striazone, tetrahydro 13 his (prop'argyloxymethyl) -5-propyl-2(l)-s-triazone d their un-' saturated analogs; tetrahydro-ifi his-(methommethyl) -5-beta-phenylethyl 2(1) s triazone. tetrahydro -'1,a bis (methoxymethyl) -5-allyl- 20 -striazone, .tetrahydrodB-bisflmethoxyme i) 5 -a.-chloropropyl2(1) -s-triazone and their analogs; tetrahydro-Lii-bis-(undecowmethyl) '-fi-a-chloropropyl-'2 (l) -s-triaaone, and the thlo analogs, incl 1- tetrahydro-1,3-

c5 his-(methoxymethyl) -'5 methyl-fi-thio-iiin -st and its analogs, tetdro 1,3 his-' (meth xy-methyl) -5- cyclohexyl-3-thio-2(l) -s" triaaone tetrahydro -l,8- his(ethoxymethyl) -5- dodecyl 2-thio-2 (l)-stion are particularly useful asmodifying acts for oellulonc mate rials. Untreated cellulcflhers tend to W. y si or by hydrogen :TI 18 or crease in use return wir-oris shape I e., catalyst capable oi efl a pH of less; and I A1- 76 wh laundered are treated with the products oi this invention they are markedly more resilient than the unmodified rayon and tend to wrinkle and crease to a lesser extent. This improved resilience or recovery from deformation is particularly important in pile fabrics such as rugs, carpets, velvets, plush fabrics, etc. Rayon fibers modified with the products of this invention are excellently suited for use as upholstery material for furniture and automobiles. Cellulpsic materials have little dye receptivity for certain types of dyes. By treating cellulosic materials with the products of this invention basic nitrogen is incorporated into the fiber and hence better dye receptivity and light fastness, etc. are obtained. The products of this invention are capable of reacting with hydroxylated polymeric materials and thus serve as cross-linking agents. For example, cellulose acetate is highly soluble in acetone but may be rendered substantially insoluble by treatment with the products of this invention. Cross-linking in this manner not only reduces solubility of the cellulose acetate but also raises the softening point and hence the safe ironing temperature of such materials. Other hydroxylated polymeric materials such as polyvinyl alcohol, hydroxylated rubber, etc. may be insolubilized by treatment with the products of this invention and thus rendered useful in a wider variety of applications. For example, polyvinyl alcohol treated with these products becomes highly resistant to water and can be used fortubes, belts, unsupported films, containers for liquids such as oils, etc., bags for foodstuffs, such as coffee, tea, bread, and the like. Polymeric materials may be'made' from the products of this invention by condensation with poly-functional compounds such as diols, dithiols. etc.-- These polymericmaterials may be used in fibers, waxes, etc. Fibers formed from them have the advantage of containing tertiary nitrogen and hence have good dyeing properties.

The above description and examp-es are intended to be illustrative only. Any modification of or variation therefrom which conforms to the spirit of the invention is intended to be included within the scope of the claims.

What is claimed is: p l. A tetrahydrotriazone having the 2 carbon attached by a double bond to a chalcogen of atomic weight less than 33, the nitrogen -attached to a monovalent hydrocarbon radical by a terminal aliphatic carbon thereof, the 1 and 3 nitrogens attached, through an oxymethyl (--CH:-O) group. to a. monovalent hydrocarbon radical by a terminal aliphatic carbon thereof, and the 4 and 6 carbons attached to hydrogen atoms.

2. A 1,3-bis-(alkoxymethyl)-5-alkyltetrahydrotriazone wherein the 2 carbon is joined, to a chalcogen of atomic weight less than 33.

3. A 1,3-bis-(alkoxymethyl)-5-alkyltetrahydrotriazone wherein the 2 carbon is Joined to oxygen.

4. Tetrahydro 1,3 bis methoxymethyl -5- methyl-2 1) -s-triazone.

5. Tetrahydro-l,3-bis- (methoxymethyl) -5-isobutyl-2(l) -s-triazone.

6. Tetrahydro 1,3 -bis (ethoxymethyl) -5- methyl-2(1) -s-triazone.

'7. Process which comprises reacting 2-oxo-5- methyltetrahydrotriazone with formaldehyde at 25-100 C. in the presence of a basic catalyst and then at 25-l00 C.'in the presence of an acidic catalyst with methanol.

8. Process which comprises reacting a tetrahydrotriazone having the 2 carbon joined to a chalcogen of atomic weight less than 33, the l .and 3 nitrogens and the 4 and 6 carbons extranuclearly to hydrogen, the 5 nitrogen to a monovalent hydrocarbon radical through a terminal aliphatic carbon thereof, with formaldehyde at 25-100" C. and then, in the presence of'an acidic catalyst, with an alcohol free from reactive groups other than hydroxyl.

9. Process which comprises reacting a 2-oxo- 5-alkyltetrahydrotriaz0ne having the extranuclear valences of the 4 and 6 carbons and thel r and 3 nitrogens satisfied by hydrogen with formaldehyde at 25-i00 C. in the presence ,of a basic .catalyst, and then at' 25-100 C. in the presence of an acidic catalyst with an alcohol wherein hydroxyl is the only reacting group.

10. Process which comprises reacting a 2-oxo- 5-alkyltetrahydrotriazone having the extranuclear valences of-the 4 and 6 carbons and the 1 and 3 nitrogens satisfied by'hydrogen with formaldehyde at 25-100 C. in the presence of a basic catalyst, and then at 25-100 C. in the presence of an acidic catalyst with an alkanol.

, Y WILLIAM JAMES BURKE. 

